Orientador: Ana Paula Rosifini Alves Claro / Banca: Sergio Schneider / Banca: Cristiane Aparacida de Assis Claro / Resumo: Fios ortodônticos são fabricados com uma série de materiais como aço inoxidável, metais, cerâmicas e polímeros. No meio bucal, eles estão sujeitos a fluídos corrosivos e variação de pH podendo levar a liberação de íons níquel nos tecidos e fluídos corpóreos. Neste estudo in vitro, filmes de carbono amorfo hidrogenado A-C:H foram depositados em fios ortodônticos empregando a técnica de PECVD para inibir a liberação de íons. O arranjo estrutural dos fios foi estudado a partir de Espectroscopia Raman e a molhabilidade avaliada medindo-se o ângulo de contato da superfície. Para avaliar a liberação de íons, os arcos ortodônticos (com e sem filme) foram montados em modelos confeccionados com resina e imersos em solução fisiológica a 37°C por 30 dias. Durante o tempo de imersão as amostras foram lavadas e/ou imersas em colutórios diariamente. Espectrofotometria de absorção atômica foi usada para medir a liberação de elementos a partir de amostras. Os resultados mostraram que o revestimento previne a liberação de Ni dos fios. O tratamento de superfície alterou o comportamento mecânico dos fios avaliados / Abstract: Orthodontics wires are made from a variety of metals such as stainless steel, metals, ceramics and polymers. In oral environment, they are subjected to aggressive fluids and pH variation that can lead to nickel ions releasing to body tissues and fluids. In this in vitro study, A:C-H films were deposited on orthodontics wires by radio-frequency plasma-enhanced chemical vapour deposition (PECVD) from inhibited nickel ions release. The structural arrangement of films was probed by Raman spectroscopy and contact angle measurements were carried out in order to evaluate the wettability of surface. To evaluate ions release, orthodontics wires (coated and uncoated) were mounted in resin mould and immersed inn physiological serum for 30 days at 37°C. During the immersion time the samples were brushed and/or immersed in mouthwashes daily. Atomic absorption spectrophotometry was used to measure the release of elements from the samples in solution. Results showed that the coating prevents Ni release of orthodontics wires. Surface treatment change mechanical properties of orthodontics wires / Mestre

Investigamos os efeitos de tamanho e do potencial de confinamento finito V0 nas taxas de espalhamento de absorção e de emissão de elétrons interagindo com os fônons longitudinais ópticos (fônons LO) de um fio quântico cilíndrico de GaAs à temperatura ambiente. Calculamos as taxas de espalhamento inter e intra-sub-banda e a taxa de espalhamento total para uma temperatura de 300 K, pois nesta temperatura o mecanismo de espalhamento dominante em semicondutores do tipo III-V é aquele devido aos fônons LO. Qualitativamente a taxa de emissão intra-sub-banda neste sistema tem o mesmo comportamento da sua correspondente em estruturas 2D. Para a absorção encontramos uma mudança suave de comportamento da taxa de absorção intra-sub-banda quando o raio do fio é da ordem do diâmetro do polaron (ou seja, da ordem de 80 ANGSTROM). Para raios pequenos ela tem um comportamento similar ao do bulk, mas para raios maiores ela cresce até atingir um máximo e depois cai monotonicamente à medida que aumentamos a energia do portador. Vimos que, o tamanho do fio e o potencial de confinamento têm grande influência na taxa de espalhamento total. / We investigated the size effects and the effects of the finite confining potential V0 on the absorption and emission scattering rates of electron interacting with longitudinal optical (LO) phonons for a cylindrical GaAs quantum wire. We calculated the inter and intrasubband total scattering rate for a temperature of 300K, because in this temperature the dominant mechanism of scattering in semiconductors III-V is that due LO phonons. Qualitatively the intrasubband emission scattering rate in this system has the same behavior of the correspondent in 2D structures. For absorption we found a smooth change in the intrasubband absorption scattering rate behavior when the radius the wire is near the polaron diameter (ie, about 80 ANGSTROM). For small radius the scattering rate has a similar behavior as that of the bulk, but for large radius it increases until reach a maximum and after ir drops monotonicaly with increase of carrier energy. We found that the size effect and the confining potential have a large influence in the total scattering rate

Nos tratamentos ortodônticos, fios de diferentes ligas metálicas são utilizados nas etapas de alinhamento, nivelamento, correção da posição molar, fechamento espacial, acabamento e retenção. Com relação às duas últimas, responsáveis pelo posicionamento adequado dos dentes superiores sobre os inferiores, a preparação requer um fio que favoreça o torque de incisão, ou seja, que apresente grande resistência e rigidez associadas à ativação de pequeno alcance. Para este fim, os fios de aços inoxidáveis austeníticos retangulares são os preferidos em razão do módulo de elasticidade elevado e boa resistência à corrosão no meio bucal. Quanto à geometria retangular, o processo de fabricação requer desenvolvimento tecnológico adequado para a produção em escala industrial de fios com as características geométricas e propriedades mecânicas para melhor adequação às necessidades de uso. Com o objetivo de se produzir fios com tais características, foi desenvolvido um laminador para a fabricação de fios retangulares com a intuito de se dispor de uma alternativa de menor custo ao processo de produção por trefilação, de custo elevado, devido a complexidade das matrizes. Além da fabricação do laminador, foram avaliados os aspectos tecnológicos que envolveram os efeitos da deformação nas propriedades mecânicas dos fios, por meio de medidas de microdurezas e ensaios em tração e de flexão. Nos testes realizados, os fios apresentaram geometria, acabamento superficial e propriedades mecânicas adequadas à sua utilização em tratamentos ortodônticos. / In orthodontic treatments, wires of different metallic alloys are used for alignment, leveling, correction of the molar position, space closing, finish and retention. With respect to finish and retention, these wires are responsible for adequate positioning of the upper teeth on the lower teeth. Wires that are subjected to incisor torque require high resistance and stiffness. For this, wires of rectangular austenitic stainless steel are used due to high modulus of elasticity and good corrosion resistance in the oral environment. Because of the rectangular geometry, wire production requires process development suitable for industrial scale manufacture with geometric characteristics and mechanical properties better adapted to the use conditions. To obtain wires with such characteristics, a rolling mill was developed for the production of rectangular wires by a rolling process with the objective of reducing cost of the cold drawing process that is currently used, which utilize complex and expensive wiredrawing dies. In addition to the rolling process itself, wire deformation, microhardness, tension and bend tests were also performed. In these tests, wire geometry, surface finish and mechanical properties were successfully adapted for use in orthodontic treatments.

Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

<p></p><p> My thesis work revolves around the ability to modify the 1,4,8,11-tetraazacyclotetradecane (cyclam) framework in order tune the electronic properties of resulting metal complexes towards real life applications. A huge direction for science and engineering is the pursuit of Moore’s Law, to constantly miniaturize electronic processes while improving their performance. With the physical limits of copper wiring being reached on nanoscale levels, alternative resources must be utilized. Naturally, the absolute limit of wiring would be on the single molecular scale. It is this idea that Chapters 1-3 are founded upon. Moving forward, I deemed three key concepts are important for success of this project: (1) the ability for modification of the molecule to be incorporated into existing technologies, (2) redox stability of the molecular complexes to allow multiple charges to pass through without losing integrity, and (3) the ability to function as a wire and allow current to pass through. Requirement (1) has been proven possible in previous work on cyclam, however (2) and (3) were yet to be shown for any cobalt tetraazamacrocyclic complex until this work.</p><p> Chapter 1 covers my first successful exploration into modification of the cylcam ligand in order to obtain favorable electronic properties. Cobalt complexes utilizing the MPC ligand (5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane) show stability upon reduction, whereas the cyclam analogues did not. In fact, [Co(MPC)(C₂Ph)₂]⁺ was the first cobalt based tetraazamacrocyclic alkynyl complex to show such redox stability without the use of heavily electron withdrawing axial ligands. It was found that this improvement of redox stability is a result of the weakened equatorial ligand field caused by the steric bulk of the phenyl substituents of the cyclam framework. This in turn led to improved axial ligand bonding and hence greater stability. This work shows the Co^III(MPC) framework can satisfy requirement (2).</p><p> Based on the results of Chapter 1, Chapter 2 realizes the idea that with improved axial ligand bond strengths in Co^III(MPC) complexes, the possibility for electronic delocalization between cobalt and the axial ligand performing as the wire is opened. A series of dinuclear Co^III(MPC) complexes, with cobalt centers linked through a butadiyndiyl bridge, were prepared. With each cobalt being identical, theoretically each should behave electrochemically similar and reduction of the complex should be a single two electron event. It is however shown that this two electron event was, in fact, split into two single electron events. The source of this result is the delocalization of the first added electron between both cobalt centers, effectively making two half-reduced metals. Therefore, the ability for Co^III(MPC) complexes to satisfy requirement (3) has been proven.</p><p> Chapter 3 expands on the results shown in Chapters 1 and 2. Where Chapter 2 showed delocalization of an electron between cobalt centers, Chapter 3 shows delocalization of a hole through cobalt between ethynylferrocene ligands. With this, all three requirements are met and the ability as Co(MPC) to function as a wire has been proven for both oxidation and reduction, both between cobalt and through cobalt.</p><p> </p><p> Chapter 4 takes a new direction, however applies the same basic principle as the previous three in modifying the cyclam ligand to achieve desired properties. Where application in electronic devices are made stable by use of the bulky MPC ligand, application towards catalysis requires an open catalytic site and weak enough axial coordination to allow the substrate to leave once reduced. Through the alkyl substitution of the cyclam ligand in Ni^II(CTMC) (5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradecane) in place of the MPC ligand, electronically donating properties of the macrocycle were maintained while opening the axial catalytic site. In this work, it was shown that reduction in steric bulk of the ligand from phenyl to ethyl to methyl, while maintaining electron donating properties, improved catalytic efficiency and all complexes were superior to Ni^II(cyclam).</p><p></p>

This project discusses the ways in which Ray Bradbury’s novel Fahrenheit 451 functions as an indictment of media culture. While many analyses of the novel focus on the text’s sweeping themes of literary censorship, this study instead centers on Bradbury’s depiction of media—particularly television—culture and the ways in which Bradbury feared it could be harmful. Although Bradbury wrote about a future society a century beyond his own, his novel serves as a remarkable reflection of his contemporaneous culture’s media consumption and gendered divisions; this thesis discusses Bradbury’s novel alongside such forces, considering the effects such influences may have had on his work.

Electrical and electronic device insulation systems experience multiple stresses while in service. Insulation design engineers usually make attempts to study the behavior of insulation under multiple stresses to keep the size and weight of the electrical insulation at a minimum. In this thesis, magnet wire insulation properties under multiple stresses are studied. Magnet wires are used for insulation in transformers, flyback transformers, solenoids, sensors, motors, adjustable speed drives etc. The magnet wire insulation under study in this work is micrometers thick, yet they are expected to provide high breakdown strength, good windability, and resistance to moisture. Accelerated life tests are performed on two different AWG 43 magnet wires. Combined Weibull Electrical-Thermal life models and Electrical-Thermal-Frequency life models were successfully verified in this work. The statistical information like lifetime characteristics, probability of failures, and lifetime percentiles determined for the two different magnet wire insulation is helpful for a better understanding of their insulation properties.

Partial discharge testing is a nondestructive method of identifying possible premature insulation breakdown. Magnet wires are used in various electrical equipment like injection coils, solenoids, small transformers and motors. Winding wires used in high voltage systems are subjected to several stresses during operation, which considerably lowers their lifetime. A prolonged combined effect of these stresses causes aging of the wires, inception of partial discharge activity, and degradation of the organic material in the enamel coating and varnish used by the manufacturer. The tests were conducted for AWG 30 and AWG 31 twisted magnet wire samples. The samples are aged under accelerated conditions of high frequency, temperature, and pulsed voltages. As well as conventional sinusoidal voltages. This thesis is focused on the results of voltage, frequency, and temperature stresses on the magnet wires. The partial discharge inception voltage (PDIV) and breakdown voltages are measured for different twisted wire samples. A software tool is utilized to study these partial discharge patterns. Evaluation of the parameters charge intensity, pulse count, and pulse phase position are presented in 2- and 3-dimensional plots.

<p> Embedding thermally conductive wires in a propellant has been known as an alternative means of increasing the burning rate of the propellant. The wires conduct heat into the propellant, preheating the material surrounding the wire and locally increasing the burning rate around the wire. As the propellant burns, a cone forms around the wire, exposing more burning surface area, which in turn increases the chamber pressure and consequently the bulk burning rate of the propellant. Likewise, embedded reactive wires have been considered in solid propellants for decades. Typically, these wires have been metal-metal reactive materials (intermetalics), but more recently metal-fluoropolymer materials have been considered. These reactive wires are consumable energetic materials that burn faster than the propellant, which allows them to expose more burning surface area by igniting the propellant faster than the burning front can proceed. Some of these reactive wire materials have also been shown to be additively manufacturable, allowing them to be printed in complex geometries, which further increases the tailorability of the burning surface profile. Previous studies on inert wires have largely focused on double base formulations, but few have considered composite propellants. These studies cast the wires against a window in order to visualize the burning that may affect the results. A few studies have also been performed with embedded reactive wires at elevated pressures, again cast against a window, which may have affected the burning dynamics by acting as an additional path for heat loss. This work studied whether the window affected the deflagration dynamics of embedded wire samples by comparing the combustion of windowed samples to full strand samples with propellant surround all sides of the wire and visualized with dynamic X-rays. High purity copper and silver wire were embedded in diameters of 0.405, 0.644, and 0.812 mm (26, 22, and 20 AWG) as inert, thermally conductive wires. A 20 wt. % active nanoscale aluminum and polyvinylidene fluoride reactive wire extruded using a 1.6 mm nozzle was also embedded for comparison to the inert wires. The windowed samples were tested in open air and in a Crawford strand burner at elevated pressures, using a high speed camera to view how the deflagration progressed along the wire against the window. The full strand samples were tested in open air using X-ray radiography to view the cone forming around the embedded wire. A burning rate enhancement was able to be measured from the burning profile around the wire. No statistically significant differences between the average measurements of windowed samples and full strand samples were found except in the case of 20 AWG Ag wire. The burning rate enhancement of the reactive wire was found to increase with increasing pressure, whereas the inert wires showed a decrease in burning rate enhancement. This effect is due to the reaction rate of the reactive wire increasing with pressure, whereas heat conduction along a metal wire is not dependent on pressure. </p>

We present in this thesis a series of studies on the physical properties of some one dimensional systems. In particular we study the low energy properties of various spin chains and a junction of Luttinger wires. For spin chains we specifically look at the role of perturbations like frustrating interactions and dimerisation in a nearest neighbour chain and the formation of magnetisation plateaus in two kinds of models; one purely theoretical and the other motivated by experiments. In our second subject of interest we study using a renormalisation group analysis the effect of spin dependent scattering at a junction of Luttinger wires. We look at the physical effects caused by the interplay of electronic interactions in the wires and the scattering processes at the junction. The thesis begins with an introductory chapter which gives a brief glimpse of the ideas and techniques used in the specific problems that we have worked on. Our work on these problems is then described in detail in chapters 25. We now present a brief summary of each of those chapters. In the second chapter we look at the ground state phase diagram of the mixed-spin sawtooth chain, i.e a system where the spins along the baseline are allowed to be different from the spins on the vertices. The spins S1 along the baseline interact with a coupling strength J1(> 0). The coupling of the spins on the vertex (S2) to the baseline spins has a strength J2. We study the phase diagram as a function of J2/J1 [1]. The model exhibits a rich variety of phases which we study using spinwave theory, exact diagonalisation and a semi-numerical perturbation theory leading to an effective Hamiltonian. The spinwave theory predicts a transition from a spiral state to a ferrimagnetic state at J2S2/2J1S1 = 1 as J2/J1 is increased. The spectrum has two branches one of which is gapless and dispersionless (at the linear order) in the spiral phase. This arises because of the infinite degeneracy of classical ground states in that phase. Numerically, we study the system using exact diagonalisation of up to 12 unit cells and S1 = 1 and S2 =1/2. We look at the variation of ground state energy, gap to the lowest excitations, and the relevant spin correlation functions in the model. This unearths a richer phase diagram than the spinwave calculation. Apart from revealing a possibility of the presence of more than one kind of spiral phases, numerical results tell us about a very interesting phase for small J2. The spin correlation function (for the spin1/2s) in this region have a property that the nextnearest-neighbour correlations are much larger than the nearest neighbour correlations. We call this phase the NNNAFM (nextnearest neighbour antiferromagnet) phase and provide an understanding of this phase by deriving an effective Hamiltonian between the spin1/2s. We also show the existence of macroscopic magnetisation jumps in the model when one looks at the system close to saturation fields. The third chapter is concerned with the formation of magnetisation plateaus in two different spin models. We show how in one model the plateaus arise because of the competition between two coupling constants, and in the other because of purely geometrical effects. In the first problem we propose [2] a class of spin Hamiltonians which include as special cases several known systems. The class of models is defined on a bipartite lattice in arbitrary dimensions and for any spin. The simplest manifestation of such models in one dimension corresponds to a ladder system with diagonal couplings (which are of the same strength as the leg couplings). The physical properties of the model are determined by the combined effects of the competition between the ”rung” coupling (J’ )and the ”leg/diagonal” coupling (J ) and the magnetic field. We show that our model can be solved exactly in a substantial region of the parameter space (J’ > 2J ) and we demonstrate the existence of magnetisation plateaus in the solvable regime. Also, by making reasonable assumptions about the spectrum in the region where we cannot solve the model exactly, we prove the existence of first order phase transitions on a plateau where the sublattice magnetisations change abruptly. We numerically investigate the ladder system mentioned above (for spin1) to confirm all our analytical predictions and present a phase diagram in the J’/J - B plane, quite a few of whose features we expect to be generically valid for all higher spins. In the second problem concerning plateaus (also discussed in chapter 3) we study the properties of a compound synthesised experimentally [3]. The essential feature of the structure of this compound which gives rise to its physical properties is the presence of two kinds of spin1/2 objects alternating with each other on a helix. One kind has an axis of anisotropy at an inclination to the helical axis (which essentially makes it an Ising spin) whereas the other is an isotropic spin1/2 object. These two spin1/2 objects interact with each other but not with their own kind. Experimentally, it was observed that in a magnetic field this material exhibits magnetisation plateaus one of which is at 1/3rd of the saturation magnetisation value. These plateaus appear when the field is along the direction of the helical axis but disappear when the field is perpendicular to that axis. The model being used for the material prior to our work could not explain the existence of these plateaus. In our work we propose a simple modification in the model Hamiltonian which is able to qualitatively explain the presence of the plateaus. We show that the existence of the plateaus can be explained using a periodic variation of the angles of inclination of the easy axes of the anisotropic spins. The experimental temperature and the fields are much lower than the magnetic coupling strength. Because of this quite a lot of the properties of the system can be studied analytically using transfer matrix methods for an effective theory involving only the anisotropic spins. Apart from the plateaus we study using this modified model other physical quantities like the specific heat, susceptibility and the entropy. We demonstrate the existence of finite entropy per spin at low temperatures for some values of the magnetic field. In chapter 4 we investigate the longstanding problem of locating the gapless points of a dimerised spin chain as the strength of dimerisation is varied. It is known that generalising Haldane’s field theoretic analysis to dimerised spin chains correctly predicts the number of the gapless points but not the exact locations (which have determined numerically for a few low values of spins). We investigate the problem of locating those points using a dimerised spin chain Hamiltonian with a ”twisted” boundary condition [4]. For a periodic chain, this ”twist” consists simply of a local rotation about the zaxis which renders the xx and yy terms on one bond negative. Such a boundary condition has been used earlier for numerical work whereby one can find the gapless points by studying the crossing points of ground states of finite chains (with the above twist) in different parity sectors (parity sectors are defined by the reflection symmetry about the twisted bond). We study the twisted Hamiltonian using two analytical methods. The modified boundary condition reduces the degeneracy of classical ground states of the chain and we get only two N´eel states as classical ground states. We use this property to identify the gapless points as points where the tunneling amplitude between these two ground states goes to zero. While one of our calculations just reproduces the results of previous field theoretic treatments, our second analytical treatment gives a direct expression for the gapless points as roots of a polynomial equation in the dimerisation parameter. This approach is found to be more accurate. We compare the two methods with the numerical method mentioned above and present results for various spin values. In the final chapter we present a study of the physics of a junction of Luttinger wires (quantum wires) with both scalar and spin scattering at the junction ([5],[6]). Earlier studies have investigated special cases of this system. The systems studied were two wire junctions with either a fully transmitting scattering matrix or one corresponding to disconnected wires. We extend the study to a junction of N wires with an arbitrary scattering matrix and a spin impurity at the junction. We study the RG flows of the Kondo coupling of the impurity spin to the electrons treating the electronic interactions and the Kondo coupling perturbatively. We analyse the various fixed points for the specific case of three wires. We find a general tendency to flow towards strong coupling when all the matrix elements of the Kondo coupling are positive at small length scales. We analyse one of the strong coupling fixed points, namely that of the maximally transmitting scattering matrix, using a 1/J perturbation theory and we find at large length scales a fixed point of disconnected wires with a vanishing Kondo coupling. In this way we obtain a picture of the RG at both short and long length scales. Also, we analyse all the fixed points using lattice models to gain an understanding of the RG flows in terms of specific couplings on the lattice. Finally, we use to bosonisation to study one particular case of scattering (the disconnected wires) in the presence of strong interactions and find that sufficiently strong interactions can stabilise a multichannel fixed point which is unstable in the weak interaction limit.